WO2020134499A1 - Filament de l'industrie du polyester destiné à un fil à coudre industriel et son procédé de préparation - Google Patents

Filament de l'industrie du polyester destiné à un fil à coudre industriel et son procédé de préparation Download PDF

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Publication number
WO2020134499A1
WO2020134499A1 PCT/CN2019/113889 CN2019113889W WO2020134499A1 WO 2020134499 A1 WO2020134499 A1 WO 2020134499A1 CN 2019113889 W CN2019113889 W CN 2019113889W WO 2020134499 A1 WO2020134499 A1 WO 2020134499A1
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Prior art keywords
acid
polyester
reaction
tert
butyl
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PCT/CN2019/113889
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English (en)
Chinese (zh)
Inventor
范红卫
王山水
王丽丽
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江苏恒力化纤股份有限公司
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Priority to US17/276,155 priority Critical patent/US11352719B2/en
Priority to JP2021537188A priority patent/JP7053961B2/ja
Publication of WO2020134499A1 publication Critical patent/WO2020134499A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C08G63/6956—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/46—Sewing-cottons or the like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/004—Oxides; Hydroxides; Oxyacids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/004—Oxides; Hydroxides; Oxyacids
    • C01G30/005—Oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Definitions

  • the invention belongs to the technical field of modified polyester fiber, and relates to a polyester industrial yarn for industrial sewing thread and a preparation method thereof.
  • Polyester fiber has developed rapidly. In the early stage of large-scale production of polyester, polyester fiber was mainly used in clothing and decorative objects. The varieties were mainly cotton and wool staple fibers and ordinary filaments. With the increase of polyester output and the demands of social development, its application has gradually expanded to industrial fields.
  • polyester industrial yarn is the same as that of ordinary polyester, but its raw materials have the characteristics of large molecular weight and narrow molecular weight distribution, as well as high breaking strength, large modulus, small elongation, heat resistance, impact resistance and fatigue resistance.
  • the advantage is that it is a good material for rubber skeletons and many industrial textiles.
  • the commonly used catalyst for the synthesis of polyester polyester is an antimony catalyst.
  • the common antimony catalysts on the market such as Sb 2 O 3 are added in a large amount during the polyester synthesis process.
  • the large amount of antimony catalysts added to the environment It also has a greater impact, which is not conducive to the environmental protection of polyester production.
  • the antimony catalyst will be converted into antimony in the polycondensation reaction, which will reduce the gray color and brightness of the polyester.
  • the greater the amount of antimony catalyst added, the polyester color The greater the impact on quality and quality, but the antimony catalyst with a small amount added cannot catalyze the reaction of all raw materials involved in polyester synthesis, and cannot meet the needs of polyester production.
  • Polyester filament sewing threads are widely used for their excellent properties such as high strength, good wear resistance, corrosion resistance, mildew resistance and jointlessness. In the field of high-end clothing, leather products, medical surgery and military products. High-grade polyester sewing thread yarn requires strength higher than 7cN/dtex, and has the characteristics of low shrinkage and low elongation.
  • polyester fiber also has some defects during use. The main reasons are poor dyeing and hygroscopicity. Polyester fiber is a hydrophobic synthetic fiber, which does not have a functional group directly combined with acid dye or basic dye molecules. Although the ester group on the polyester fiber can form a hydrogen bond with the disperse dye, it is still difficult for the dye molecule to enter the fiber due to the tight molecular chain structure of the polyester. Therefore, when dyeing polyester, usually only disperse dyes can be used, and they must be dyed under high temperature and high pressure or with the help of a carrier, resulting in a monotonous color of the final polyester textile, high energy consumption, and low dyeing rate. .
  • the purpose of the present invention is to overcome the above-mentioned problems in the prior art, to provide a polyester industrial yarn for industrial sewing thread with good dyeing performance and high quality and a preparation method thereof.
  • polyester industrial yarn for industrial sewing thread which is obtained by solidified polycondensation, thickening, melting, metering, extrusion, cooling, oiling, stretching, heat setting and winding of modified polyester melt Polyester industrial yarn for industrial sewing thread;
  • the preparation method of the modified polyester before solid phase polycondensation and tackification is: mixing terephthalic acid, ethylene glycol, a dibasic acid with pendant tert-butyl groups, a glycol with pendant trimethylsilyl groups and doping Modified Sb 2 O 3 powder is mixed uniformly and then esterified and then polycondensed;
  • the dibasic acids with pendant tert-butyl groups are 5-tert-butyl-1,3-phthalic acid, 2-tert-butyl-1,6-hexanedicarboxylic acid, 3-tert-butyl-1,6-hexane
  • the structural formula of dicarboxylic acid or 2,5-di-tert-butyl-1,6-hexanedicarboxylic acid, glycol with pendant trimethylsilyl groups is as follows:
  • R is -CH 2 -, -CH(CH 3 )- or -C((CH 3 ) 2 )-;
  • the dibasic acid with pendant tert-butyl group and the glycol with pendant trimethylsilyl group are used to modify the polyester, which easily causes changes in the activity of the main chain, thereby changing the interaction force between the chain units ,
  • the distance between the molecular chain units will also change accordingly, increasing the free volume of the modified polyester cavity;
  • disperse dyes are a class of dyes with relatively small molecules and no water-soluble groups in the structure, which are mostly in the form of particles Exist, the particle size is between several hundred nanometers and one micrometer.
  • the temperature of the dyeing bath needs to be increased to 120 °C .
  • the side group movement is more severe than that of the molecular chain.
  • the free volume of the cavity formed by the side group is larger than the free volume of the slit formed by the molecular chain, the diffusion rate of the particulate dye into the fiber is significantly increased, which significantly reduces the The difficulty of dye molecules penetrating into the interior of the modified polyester, improve the dyeing performance of the modified polyester, reduce the dyeing temperature, shorten the dyeing time, reduce energy consumption, and improve the dyeing rate of the modified polyester;
  • the process of Sb 2 O 3 doping and modification is as follows: first, the solution containing the metal ion M x+ and the solution containing Sb 3+ are mixed uniformly, then the precipitant is added dropwise until the pH of the mixed solution is 9-10, and finally the calcined precipitate The product is crushed; the metal ion M x+ is more than one of Mg 2+ , Ca 2+ , Ba 2+ and Zn 2+ ;
  • the invention realizes the doping and blending of a metal oxide with a certain catalytic activity and antimony trioxide by mixing the metal ion M x+ solution and the Sb 3+ solution first and then precipitating and finally calcining. It is one or more of MgO, CaO, BaO and ZnO. After the metal oxide of the present invention is doped with antimony trioxide, the metal oxide inhibits the crystallization of antimony trioxide and the cubic antimony trioxide grains.
  • the present invention can realize the catalytic synthesis of polyester at a low Sb 2 O 3 addition amount, which is conducive to environmental protection production and guarantees the quality of the synthesized polyester, and thus can guarantee the quality of the final product.
  • the raw material olefin corresponds to 3-trimethylsilyl-3 -Methacrylic acid and 3-trimethylsilyl-3,3-dimethylpropene;
  • the synthesis method of the 2-tert-butyl-1,6-hexanedicarboxylic acid, 3-tert-butyl-1,6-hexanedicarboxylic acid and 2,5-di-tert-butyl-1,6-hexanedicarboxylic acid is :
  • the molar ratio of tungstic acid, raw material alcohol and hydrogen peroxide is 1:30 ⁇ 40:120 ⁇ 150;
  • Raw material alcohols corresponding to the 2-tert-butyl-1,6-hexanedicarboxylic acid, 3-tert-butyl-1,6-hexanedicarboxylic acid and 2,5-di-tert-butyl-1,6-hexanedicarboxylic acid These are 2-tert-butylcyclohexanol, 4-tert-butylcyclohexanol and 2,4-di-tert-butylcyclohexanol.
  • the concentration of the metal ion-containing M x+ solution is 0.5 to 1.0 mol%, the solvent is water, and the anion in the solution is NO 3 - ;
  • the solution containing Sb 3+ is a solution of Sb 2 O 3 with a concentration of 5 to 10 mol%, and the solvent is oxalic acid;
  • the precipitant is ammonia with a concentration of 2 mol/L; when precipitation starts, the metal ions M x+ and Sb 3 in the mixed solution
  • the molar ratio of + is 1 ⁇ 3:100; Sb 2 O 3 is currently the most cost-effective polyester catalyst.
  • the present invention inhibits antimony trioxide (Sb 2 O 3 ) by infiltrating metal oxides (ie M 2 O X ) Crystallization and the growth of cubic antimony trioxide grains, and at the same time, the metal ion M x+ will replace antimony and enter the lattice position of antimony, making the antimony trioxide crystal defects, so as to improve the catalytic activity of antimony trioxide; such as If the amount of doped metal oxide is too small (the molar ratio is too low), the effect on the antimony trioxide grains is too low, and too much (the molar ratio is too high) will make the main body of the catalyst Sb 3+ decrease by a large extent, all of which will increase the The catalytic activity of antimony trioxide is unfavorable;
  • the drying temperature is 105 ⁇ 110°C, and the time is 2 ⁇ 3h; the process of the calcination is: first warm up to 400°C, then keep warm for 2 ⁇ 3h, and then raise the temperature to 900°C After heat preservation for 1 ⁇ 2h, and finally cooling in air;
  • Sb 2 O 3 is pulverized to obtain a powder with an average particle size of less than 0.5 ⁇ m.
  • the preparation steps of the modified polyester before solid-phase polycondensation and tackification are as follows:
  • esterification reaction is carried out under pressure in a nitrogen atmosphere.
  • the pressure is from normal pressure to 0.3 MPa.
  • the temperature of the esterification reaction is 250 to 260°C. When the amount of water distilled in the esterification reaction is When it reaches more than 90% of the theoretical value, it is the end point of esterification reaction;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 500 Pa or less within 30 to 50 minutes.
  • the reaction temperature is 250 to 260°C and the reaction time is 30 ⁇ 50min, and then continue to evacuate to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to below 100Pa absolute pressure, the reaction temperature is 270 ⁇ 282°C, and the reaction time is 50 ⁇ 90min.
  • polyester industrial yarn for industrial sewing thread as described above, the terephthalic acid, ethylene glycol, dibasic acid with pendant tert-butyl group and glycol with pendant trimethylsilyl group
  • the molar ratio is 1:1.2 ⁇ 2.0:0.02 ⁇ 0.03:0.01 ⁇ 0.02;
  • the addition amount of the tertiary butyl group-bearing dibasic acid and trimethylsilyl group-bearing diol is preferably in this range, which can not only ensure that the modified fiber has good mechanical properties and crystallinity, but also The dyeing performance of the fiber is significantly improved, which is beneficial to the production and application of the fiber.
  • the addition amount of the tertiary butyl group-containing dibasic acid and trimethylsilyl group-containing diol can be adjusted according to actual needs, but the adjustment range is not suitable If the amount is too high, the regularity of the polyester macromolecular structure will be destroyed too much, and the crystallinity and mechanical properties of the fiber will be affected too much, which is not conducive to the production and application of the fiber. If the amount is too low, the dyeing effect will not be improved significantly. ;
  • the added amounts of the doped and modified Sb 2 O 3 powder, matting agent and stabilizer are 0.012 to 0.015 wt%, 0.20 to 0.25 wt% and 0.01 to 0.05 wt% of the added amount of terephthalic acid;
  • the amount of Sb 2 O 3 added in the synthesis of polyester is usually 0.02 ⁇ 0.04wt% of the amount of terephthalic acid, and the amount of antimony catalyst is high.
  • the present invention is by doping Sb 2 O 3 modification, increases the activity of Sb 2 O 3, Therefore, the amount of Sb 2 O 3 added during polyester synthesis is significantly reduced.
  • the matting agent is titanium dioxide
  • the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
  • the intrinsic viscosity of the modified polyester after the solid-phase polycondensation and thickening is 1.0 to 1.2 dL/g.
  • the preparation method of the polyester industrial yarn for industrial sewing thread as described above, the spinning process parameters of the polyester industrial yarn for industrial sewing thread are as follows:
  • the process parameters of stretching and heat setting are:
  • the present invention also provides a polyester industrial yarn for industrial sewing thread prepared by using the preparation method of the polyester industrial yarn for industrial sewing thread as described above, and the material is modified polyester;
  • the molecular chain of the modified polyester includes a terephthalic acid segment, an ethylene glycol segment, a dibasic acid segment with pendant tert-butyl groups, and a diol segment with pendant trimethylsilyl groups;
  • the doped and modified Sb 2 O 3 powder is dispersed in the modified polyester.
  • the polyester industrial yarn for industrial sewing thread has a monofilament fineness of 2 to 3 dtex, a multifilament fineness of 150 to 300 dtex, a breaking strength ⁇ 8.0 cN/dtex, and a linear density
  • the deviation rate is ⁇ 1.5%
  • the breaking strength CV value is less than or equal to 3.0%
  • the breaking elongation rate is 13.0 to 16.5%
  • the breaking elongation CV value is less than 8.0%
  • the elongation rate at 4.0 cN/dtex load is 5.5 to 7.0%.
  • Dry heat shrinkage rate at 177°C ⁇ 10min ⁇ 0.05cN/dtex is 6.8 ⁇ 9.2%, network degree is (5 ⁇ 8) ⁇ 2 pcs/m, oil content is 0.6 ⁇ 0.2wt%; the invention is used in industry
  • the mechanical properties of the polyester industrial yarn of the sewing thread are comparable to the existing technology, and the mechanical properties have not been reduced due to modification;
  • the dyeing rate of modified polyester FDY yarn at a temperature of 130°C is 88.8 ⁇ 91.2%, and the K/S value is 24.07 ⁇ 26.12; under the same test conditions, the comparison sample is at a temperature of 130°C Has a dyeing rate of 84.3% and a K/S value of 21.56.
  • the difference between the comparative sample and the polyester industrial yarn of the present invention is only that its material is a dibasic acid segment with pendant t-butyl groups not introduced into the polyester molecular chain And a diol segment with pendant trimethylsilyl groups.
  • the dibasic acid with pendant tert-butyl group and the glycol with pendant trimethylsilyl group are used as reactants and the doped modified Sb 2 O 3 powder is used as a catalyst during the synthesis of polyester.
  • Polyester industrial yarn made by solid-phase polycondensation tackification and spinning process for industrial sewing thread improves the dyeing effect of polyester industrial yarn, and at the same time guarantees the quality of the produced polyester industrial yarn, as follows:
  • the macromolecular chains in the polymer are not completely tightly packed, there are always gaps between the macromolecular chains, and the volume of this part of the void is the free volume.
  • the permeability and diffusivity of the small molecule are related to the size of the void (ie, the size of the free volume) in the polymer structure.
  • the larger the size of the free volume the higher the permeability of small molecules and the better the diffusibility.
  • the free volume is divided into the free volume of the cavity and the free volume of the slit.
  • the free volume of the cavity has a larger space size than the free volume of the slit. For the increase of the permeability of small molecules, increasing the free volume of the cavity is more than increasing the free volume of the slit. The effect is more obvious.
  • the size and type of free volume mainly depend on the structure of the polymer.
  • the main factors that affect the structure of the polymer are steric hindrance, side group size, and side group structure.
  • steric hindrance When a position on the polymer main chain is substituted with a pendant group, it will inevitably cause changes in the main chain activity, thereby changing the interaction force between chains, and the distance between chains will also change accordingly.
  • the molecular chain of this regular tetrahedron arrangement is relatively zigzag, and the free volume of the cavity is significantly increased, which can significantly improve the permeability and diffusivity of small molecules; when the H atom on the benzene ring of isophthalic acid or When the H atom on the adipic acid methylene group is replaced by a long-chain branched substituent, the main increase is the free volume of the slit, the increase is small, and the effect of improving the permeability and diffusivity of small molecules is limited. Due to the low rigidity of the long-chain branched substituents, the molecular chains are prone to entanglement, which is not conducive to the increase in free volume.
  • the diacid with pendant tert-butyl group of the present invention is 5-tert-butyl-1,3-phthalic acid, 2-tert-butyl-1,6-hexanedicarboxylic acid, 3-tert-butyl-1, 6-adipic acid or 2,5-di-tert-butyl-1,6-hexanedicarboxylic acid, including 2-tert-butyl-1,6-hexanedicarboxylic acid, 3-tert-butyl-1,6-hexanedicarboxylic acid
  • adipic acid which is a kind of fatty acid, its rigidity is less than 5-tert-butyl-1,3-phthalic acid, which is conducive to improving polyester
  • the flexibility of the segment, the presence of tert-butyl in the dibasic acid with pendant tert-butyl group will cause changes in the activity
  • tert-butyl occupies a larger space position, and will obtain a larger free volume in the manner of molecular chain arrangement;
  • tertiary butyl increases the void free volume, while long-chain branched substituents increase the slit free volume, on the other hand, tertiary butyl is more rigid than long-chain branched substituents, reducing The entanglement between the molecular chains, so the longer-branched tertiary butyl substituent has more free volume in the way the molecular chains are arranged.
  • the dibasic acid with pendant tert-butyl group is 5-tert-butyl-1,3-phthalic acid
  • the benzene ring linked by meta-dicarboxylic acid will form a larger asymmetric segment, not only The steric hindrance of the migration between the segments is increased and the steric hindrance of the rotation around the meta link is increased in the segment.
  • the introduction of the meta isomer is conducive to the increase of the free volume. The introduction increases the void free volume of the modified polyester.
  • R is -CH 2 -(glycol with pendant trimethylsilyl group is 3-trimethylsilyl-1,2-propanediol), -CH(CH 3 )-(discharged with pendant trimethylsilyl group)
  • Monohydric alcohol is 3-trisilyl-3-methyl-1,2-propanediol) or -C((CH 3 ) 2 )-(glycol with pendant trimethylsilyl groups is 3-trisilyl-3 , 3-dimethyl-1,2-propanediol).
  • the C atoms in the main chain are arranged in a zigzag pattern.
  • the H atom of a methylene group on the main chain is replaced by a methyl group (-CH 3 )
  • the The C atom is not in the same plane as the main chain C atom, so the four sp3 hybrid orbitals on the center C overlap with the empty orbitals on the surrounding four C atoms, forming four identical ⁇ bonds, arranged in a regular tetrahedron
  • the four carbon atoms are located at the four vertices of the regular tetrahedron.
  • the molecular chain has a much larger void free volume, which can significantly improve the permeability and diffusivity of small molecules.
  • the bond length of the carbon-silicon bond in the trimethylsilyl group is greater than that of the carbon-carbon bond.
  • the bond length is conducive to the free rotation of the atoms, which in turn is conducive to increasing the free volume of the cavity; when the H atom on a methylene group on the main chain is replaced by a long-chain branched substituent, the main increase is the free volume of the slit
  • the increase is small, and the effect of improving the permeability and diffusivity of small molecules is limited.
  • the molecular chains are prone to entanglement, which is not conducive to the increase of free volume.
  • trimethylsilyl occupies a larger space position, and will obtain a larger free volume in the manner of molecular chain arrangement; with long branched chains Compared with substituents, on the one hand, the increased free volume of trimethylsilyl is more of the void free volume, while the increased free volume of long-chain branched substituents is more of the slit free volume, on the other hand, of trimethylsilyl
  • the rigidity is greater than the long-chain branched substituents, which reduces the entanglement between the molecular chains, so the trimethylsilyl longer branched-chain substituents have more free volume in the way the molecular chains are arranged.
  • the introduction of diols with pendant trimethylsilyl groups also increases the free volume of the modified polyester, especially the free volume of the void.
  • the increase in the free volume of the cavity will make it easier for water or other molecules such as dyes to penetrate into the interior of the modified polyester macromolecule, which will have a positive effect on the dyeing of the modified polyester, etc.
  • the problem of excessive difficulty in dyeing reduces the dyeing temperature, shortens the dyeing time, reduces energy consumption, and also increases the dyeing rate of the fiber.
  • the doped and modified Sb 2 O 3 powder used in the synthesis of polyester is mainly used as a catalyst.
  • the existing polyester catalysts are mainly based on antimony compounds, such as antimony trioxide, ethylene glycol antimony and antimony acetate.
  • antimony compounds such as antimony trioxide, ethylene glycol antimony and antimony acetate.
  • the addition of antimony in polyester synthesis in industry is greater than 200ppm. Since antimony is a heavy metal, the progress of the times has imposed more and more strict restrictions on antimony catalysts.
  • titanium-based catalysis has been applied, due to various aspects such as color and activity control For reasons, it is still impossible to replace the antimony system in a short time.
  • the catalytic activity of the catalyst is proportional to the specific surface area S g of the catalyst, the internal surface utilization rate f, and the activity r s per unit surface area.
  • its catalytic activity depends on the specific surface area S g of the catalyst and the internal surface
  • the utilization rate f and the activity r s per unit surface area of the catalyst are constant, the larger the specific surface area, the higher the catalytic activity.
  • the invention realizes the doping and blending of a metal oxide with a certain catalytic polycondensation reaction activity and antimony trioxide by solution blending, co-precipitation and calcination.
  • the metal oxide is one of MgO, CaO, BaO and ZnO
  • MgO, CaO, BaO, ZnO are all white crystals, as a polyester catalyst does not bring about changes in color.
  • metal oxides on antimony trioxide are mainly reflected in: on the one hand, metal oxides will inhibit the crystallization of antimony trioxide and the growth of cubic antimony trioxide grains, making the specific surface area of the antimony trioxide catalyst
  • the increase of S g improves the catalytic activity of antimony trioxide; on the other hand, the metal will replace antimony with the same crystal and enter the lattice position of antimony, which causes defects in the antimony trioxide crystal, changes in crystal morphology, and smaller grain size
  • the specific surface area S g increases, and at the same time, the metal is enriched on some crystal surfaces, so that the active r s per unit surface area is increased, and the catalytic activity of antimony trioxide is improved.
  • the invention improves the catalytic activity of antimony trioxide by doping antimony trioxide to a certain extent.
  • the increase in the catalytic activity of antimony trioxide is beneficial to reduce the amount of antimony trioxide.
  • the use of antimony trioxide with metal oxides can reduce the use of antimony trioxide by more than 30%, effectively solving the current addition of antimony trioxide A big problem, at the same time, it can meet the needs of polyester production and ensure the quality of the produced PET, and then the quality of the final product.
  • the preparation method of the polyester industrial yarn for industrial sewing thread of the present invention improves the specific surface area S g of antimony trioxide by doping and modifying the antimony trioxide with a metal oxide having a certain catalytic activity
  • the activity r s per unit surface area improves the catalytic activity of antimony trioxide and improves the polymerization efficiency; furthermore, it can reduce the amount of antimony catalyst added when synthesizing polyester while meeting the needs of polyester production, effectively reducing its
  • the antimony emission of the finished fiber is conducive to the realization of environmental protection production;
  • the preparation method of the polyester industrial yarn for industrial sewing thread of the present invention has a simple process and low cost.
  • a dibasic acid with a tertiary butyl pendant group and a dimethacrylate with a trimethylsilyl side group into the polyester
  • the alcohol modifies the polyester, which reduces the dyeing temperature, shortens the dyeing time, improves the dyeing rate of the fiber, and reduces energy consumption;
  • the polyester industrial yarn for industrial sewing thread of the present invention has excellent mechanical properties and dyeing properties, and has good application prospects.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • the dried product is first heated to 400°C and then kept for 2.5h, then heated to 900°C and kept for 1.5h, and finally cooled in air and pulverized to obtain a doped modified particle with an average particle size of 0.4 microns Sb 2 O 3 powder;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 400 Pa, the reaction temperature is 250 °C, the reaction time is 40 min, and then the pumping is continued.
  • Vacuum to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 80Pa, a reaction temperature of 272°C, and a reaction time of 65min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and wound by modified polycondensation of polyester, solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.0dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 2dtex, multifilament fineness is 150dtex, breaking strength is 8.0cN/dtex, linear density deviation rate is -0.6%,
  • the breaking strength CV value is 2.8%, the breaking elongation rate is 14.05%, the breaking elongation CV value is 8.0%, the elongation rate under 4.0cN/dtex load is 7.0%, under the condition of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 7.6%, the network degree is 5 pieces/m, and the oil content is 0.4wt%; the dyeing rate of polyester industrial yarn used for industrial sewing thread at a temperature of 130°C is 89.17%, K/
  • the S value is 26.12.
  • a preparation method of polyester industrial yarn for industrial sewing thread the preparation steps are basically the same as in Example 1, except that 5-tert-butyl-1,3-phthalic acid and 3-trimethylsilyl are not added -1,2-Propanediol and doped modified Sb 2 O 3 powder, that is, without modifying the polyester, the monofilament fineness of the polyester industrial yarn finally used for industrial sewing thread is 2dtex, and the multifilament fineness 150dtex, breaking strength 8.1cN/dtex, linear density deviation rate -0.6%, breaking strength CV value 2.8%, breaking elongation rate 13.75%, breaking elongation CV value 8.0%, 4.0cN/dtex load The elongation rate is 7.0%, the dry heat shrinkage rate is 7.6% at 177°C ⁇ 10min ⁇ 0.05cN/dtex, the network degree is 5 pieces/m, and the oil content is 0.4wt%; Under the same test conditions, the dyeing rate of polyester industrial yarn used in industrial sewing threads at a temperature of 130°C was 86.3
  • the free volume of the cavity is increased, which reduces the difficulty of the dye molecules entering the fiber, so that the dyeing rate of the fiber is greatly improved.
  • the present invention adds doped modified Sb 2 O 3 powder when synthesizing polyester Significantly reduce the amount of antimony-based catalyst added, achieve environmentally friendly production, and ensure product quality.
  • a preparation method of polyester industrial yarn for industrial sewing thread the preparation steps are basically the same as in Example 1, except that in step (1), 1,2-dodecyldiol is used instead of 3-trimethylsilyl -1,2-Propanediol and 5-tert-butyl-1,3-phthalic acid, the resulting polyester industrial yarn for industrial sewing thread has a monofilament fineness of 2dtex, a multifilament fineness of 150dtex, and a breaking strength of 8.2cN/dtex, linear density deviation rate is -0.6%, breaking strength CV value is 2.8%, breaking elongation rate is 13.53%, breaking elongation CV value is 8.0%, 4.0cN/dtex load elongation rate is 7.0 %, dry heat shrinkage rate at 177°C ⁇ 10min ⁇ 0.05cN/dtex is 7.6%, network degree is 5 pieces/m, and oil content is 0.4wt%; under the same test conditions as in Example 1 The dyeing rate of polyester industrial yarn used in industrial sewing thread at a
  • polyester industrial yarn for industrial sewing thread is as follows:
  • the Ca(NO 3 ) 2 aqueous solution with a concentration of 0.5 mol% and the Sb 2 O 3 solution with a concentration of 5 mol% are mixed uniformly.
  • the solvent of the Sb 2 O 3 solution is oxalic acid, and Ca 2 in the mixed solution
  • the molar ratio of + to Sb 3+ is 1:100;
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise until the pH of the mixed solution is 10 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 110° C. for 2 hours;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 400 Pa, the reaction temperature is 250 °C, the reaction time is 40 min, and then the pumping is continued.
  • Vacuum to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 80Pa, a reaction temperature of 270°C, and a reaction time of 50min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and wound by modified polycondensation of polyester, solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.1dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 2dtex, multifilament fineness is 300dtex, breaking strength is 8.3cN/dtex, linear density deviation rate is -1.5%,
  • the breaking strength CV value is 2.8%, the breaking elongation rate is 13.0%, the breaking elongation CV value is 7.9%, the elongation rate under 4.0cN/dtex load is 6.5%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 7.7%, the network degree is 3 pieces/m, and the oil content is 0.6wt%; the dyeing rate of polyester industrial yarn used for industrial sewing threads at a temperature of 130°C is 88.8%, K/
  • the S value is 25.32.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise to a pH of 9.5 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 105°C for 3 hours;
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 450 Pa within 45 minutes, the reaction temperature is 256°C, the reaction time is 50 minutes, and then the pumping continues Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 100Pa, the reaction temperature is 275 °C, the reaction time is 60min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and wound by modified polycondensation of polyester, solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.0dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 2.6dtex, multifilament fineness is 150dtex, breaking strength is 8.1cN/dtex, linear density deviation rate is 0%,
  • the breaking strength CV value is 3.0%, the breaking elongation rate is 13.0%, the breaking elongation CV value is 7.95%, and the elongation rate under 4.0cN/dtex load is 5.5%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 9.2%, the network degree is 7 pieces/m, and the oil content is 0.6wt%; the dyeing rate of polyester industrial yarn used in industrial sewing thread at a temperature of 130°C is 88.8%, K/
  • the S value is 24.07.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise to a pH of 10 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 110°C and a time of 2.5 h;
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 420 Pa, the reaction temperature is 260 °C, the reaction time is 35 min, and then continue to pump Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 85Pa, the reaction temperature is 270 °C, the reaction time is 90min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and wound by modified polycondensation of polyester, solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.0dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 2.3dtex, multifilament fineness is 200dtex, breaking strength is 8.5cN/dtex, linear density deviation rate is 1.0%,
  • the breaking strength CV value is 2.8%, the breaking elongation rate is 16.5%, the breaking elongation CV value is 7.6%, the elongation rate under 4.0cN/dtex load is 5.5%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 6.8%, the network degree is 8 pieces/m, and the oil content is 0.8wt%; the dyeing rate of polyester industrial yarn used for industrial sewing threads at a temperature of 130°C is 91.2%, K/ The S value is 24.07.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise to a pH of 10 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 110°C and a time of 2.5 h;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 500 Pa within 30 minutes, the reaction temperature is 256 °C, the reaction time is 45 minutes, and then continue to pump Vacuum to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to 88Pa absolute pressure, the reaction temperature is 280 °C, the reaction time is 75min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and winding modified polyester melts, and solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.2dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 3dtex, multifilament fineness is 260dtex, breaking strength is 8.5cN/dtex, linear density deviation rate is 1.5%, breaking The strength CV value is 2.7%, the elongation at break is 14.8%, the elongation at break CV is 7.7%, the elongation at 4.0 cN/dtex load is 7.0%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex Dry heat shrinkage rate is 6.8%, network degree is 10 pieces/m, oil content is 0.6wt%; polyester industrial yarn used for industrial sewing thread has a dyeing rate of 89.29% at a temperature of 130°C, K/S The value is 26.12.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • the aqueous solution and the Sb 2 O 3 solution with a concentration of 8 mol% are mixed evenly.
  • the solvent of the Sb 2 O 3 solution is oxalic acid, and the molar ratio of M x+ to Sb 3+ in the mixed solution is 2.5:100;
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise until the pH of the mixed solution is 10 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 105°C for 3 hours;
  • the dried product is first heated to 400°C and kept for 3h, then heated to 900°C and kept for 1.5h, and finally cooled in the air and pulverized to obtain doped modified Sb with an average particle size of 0.4 microns 2 O 3 powder;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is pumped smoothly from normal pressure to an absolute pressure of 490 Pa, the reaction temperature is 260 °C, the reaction time is 50 min, and then the pumping is continued.
  • Vacuum to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 90Pa, a reaction temperature of 275°C, and a reaction time of 50min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and winding modified polyester melts, and solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.2dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 3dtex, multifilament fineness is 300dtex, breaking strength is 8.0cN/dtex, linear density deviation rate is -1.5%,
  • the breaking strength CV value is 3.0%, the breaking elongation rate is 16.5%, the breaking elongation CV value is 7.9%, the elongation rate under 4.0cN/dtex load is 6.5%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 6.8%, the network degree is 8 pieces/m, and the oil content is 0.4wt%; the dyeing rate of polyester industrial yarn used for industrial sewing thread at a temperature of 130°C is 91.2%, K/ The S value is 24.59.
  • polyester industrial yarn for industrial sewing thread is as follows:
  • Mg(NO 3 ) 2 aqueous solution, Ba(NO 3 ) 2 aqueous solution and Ca(NO 3 ) 2 aqueous solution are all mixed at a concentration ratio of 0.5mol% in a volume ratio of 1:1:1 to obtain metal ion-containing M
  • the aqueous solution of x+ , the aqueous solution containing metal ions M x+ is mixed with the solution of Sb 2 O 3 at a concentration of 10 mol%, the solvent of the solution of Sb 2 O 3 is oxalic acid, and the moles of metal ions M x+ and Sb 3+ in the mixed solution
  • the ratio is 2:100;
  • Aqueous ammonia with a concentration of 2 mol/L is added dropwise to a pH of 9 to obtain a precipitated product, and then the precipitated product is washed and dried at a drying temperature of 108°C and a time of 2.5 h;
  • the polycondensation reaction in the low vacuum stage starts under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 440 Pa, the reaction temperature is 260 °C, the reaction time is 40 minutes, and then continue to pump Vacuum to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 95Pa, a reaction temperature of 282°C, and a reaction time of 70min;
  • Polyester industrial yarn used for industrial sewing thread is prepared by solid-phase polycondensation of thickened, melted, metered, extruded, cooled, oiled, stretched, heat-set and wound by modified polycondensation of polyester, solid-phase polycondensation is increased
  • the intrinsic viscosity of the modified polyester after sticking is 1.0dL/g, and the spinning process parameters are as follows:
  • the process parameters of stretching and heat setting are:
  • the final polyester industrial yarn material used for industrial sewing thread is modified polyester, its monofilament fineness is 2.5dtex, multifilament fineness is 150dtex, breaking strength is 8.2cN/dtex, linear density deviation rate is 1.5%,
  • the breaking strength CV value is 2.8%, the breaking elongation rate is 15.0%, the breaking elongation CV value is 7.8%, the elongation rate under 4.0 cN/dtex load is 7.0%, under the conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex
  • the dry heat shrinkage rate is 9.2%, the network degree is 6 pieces/m, and the oil content is 0.6wt%; the dyeing rate of polyester industrial yarn used in industrial sewing thread at a temperature of 130°C is 90.28%, K/ The S value is 26.12.

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Abstract

L'invention concerne un filament de l'industrie du polyester destiné à un fil à coudre industriel et son procédé de préparation. Une masse fondue de polyester modifié est soumise à une polycondensation en phase solide et à une viscosification, ainsi qu'à un procédé de filature, afin de préparer un filament de l'industrie du polyester destiné à un fil à coudre industriel. Un procédé de préparation du polyester modifié avant la polycondensation en phase solide et la viscosification consiste : à mélanger uniformement de l'acide téréphtalique, de l'éthylène glycol, de l'acide dibasique ayant un groupe tert-butyle pendant, de l'alcool dihydrique ayant un groupe triméthylsilicium pendant, et de la poudre de Sb2O3 dopée à l'oxyde métallique et modifiée par ledit un oxyde métallique, puis à réaliser séquentiellement une réaction d'estérification et d'une réaction de condensation. L'acide dibasique ayant le groupe tert-butyle pendant est l'acide 5-tert-butyl-1,3-phtalique, l'acide 2-tert-butyl-1,6-adipique, l'acide 3-tert-butyl-1,6-adipique ou l'acide 2,5-di-tert-butyl-1,6-adipique. Le filament de l'industrie du polyester préparé présente une vitesse de teinture élevée et une valeur K/S élevée. Le procédé de l'invention est un processus simple, et le filament de l'industrie du polyester ainsi préparé présente une bonne aptitude à la teinture.
PCT/CN2019/113889 2018-12-27 2019-10-29 Filament de l'industrie du polyester destiné à un fil à coudre industriel et son procédé de préparation WO2020134499A1 (fr)

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US17/276,155 US11352719B2 (en) 2018-12-27 2019-10-29 Polyester yarn for industrial sewing thread and preparing method thereof
JP2021537188A JP7053961B2 (ja) 2018-12-27 2019-10-29 工業用ミシン糸に用いられるポリエステル工業用糸の製造方法

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CN201811614107.XA CN109735937B (zh) 2018-12-27 2018-12-27 用于工业缝纫线的涤纶工业丝及其制备方法
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